Polymer containing 9-oxo-9-phosphafluorene-2,7-diyl skeleton in backbone and process for producing the same

ABSTRACT

A polymer containing in the backbone a 9-oxo-9-phosphafluorene-2,7-diyl skeleton or a combination of the skeleton with a vinylene skeleton or arylene skeleton. The polymer is utilizable as, e.g., a component of a luminescent element or electrochromic element.  
     The polymer is obtained by subjecting a 2,7-dihalo-9-oxo-9-phosphafluorene to polycondensation with dehalogenation, or to reaction with arylenebisboronic acid and polycondensation, or to polycondensation with an olefin.

TECHNICAL FIELD

[0001] The present invention relates to a polymer containing in thebackbone a 9-oxo-9-phosphafluorene-2,7-diyl skeleton that is condensedwith a phosphorus atom. Precisely, the invention relates to such apolymer that contains in the backbone the skeleton or a combination ofthe skeleton and a vinylene or arylene skeleton, and to a process forproducing the polymer, as well as to use of the polymer for a componentof a luminescent element or electrochromic element.

BACKGROUND ART

[0002] Methods of producing 9-oxo-9-phosphafluorene-based chemicals areknown in the art. However, a polymer that contains in the backbone a9-oxo-9-phosphafluorene-2,7-diyl skeleton or a combination of theskeleton and a vinylene or arylene skeleton, and a process for producingit, as well as the behavior of the polymer for a component of aluminescent element or electrochromic element are unknown. In addition,2,7-dihalo-9-alkyl-9-oxo-9-phosphafluorene compounds that are used asthe starting monomer for the polymer, and a process for producing themare also unknown.

DISCLOSURE OF THE INVENTION

[0003] One object of the present invention is to provide a polymer thatcontains in the backbone a 9-oxo-9-phosphafluorene-2,7-diyl skeleton ora combination of the skeleton and a vinylene or arylene skeleton, and toprovide a process for producing the polymer. The polymer is utilizableas, for example, a component of a luminescent element or electrochromicelement. Another object of the invention is to provide a2,7-dihalo-9-alkyl-9-oxo-9-phosphafluorene compound which is used as thestarting monomer for the polymer, and a process for producing thecompound.

BEST MODES OF CARRYING OUT THE INVENTION

[0004] The invention relates to a polymer that contains in the backbonea 9-oxo-9-phosphafluorene-2,7-diyl skeleton and a vinylene skeleton ofthe following general formula [I], to a process for producing thepolymer, and to a luminescent element or an electrochromic element thatcontain the polymer.

[0005] [wherein —Q— represents a single bond, —Ar— (Ar is an arylenegroup), or a vinylene group of the following general formula [II]:

[0006] (in which R′ represents a hydrogen atom, anoptionally-substituted alkyl, cycloalkyl, aryl or aralkyl group, a cyanogroup, or an alkoxycarbonyl group, and it may bond to any carbon of theolefin chain in the formula);

[0007] R represents a hydrogen atom, or an optionally-substituted alkyl,cycloalkyl, aralkyl, aryl, alkoxy, cycloalkyloxy, aralkyloxy or aryloxygroup; and n indicates an integer of from 3 to 30000].

[0008] Formula [I] where —Q— is a single bond represents a polymer thatcontains in the backbone a 9-oxo-9-phosphafluorene-2,7-diyl skeleton ofthe following general formula [III]:

[0009] (wherein R and n have the same meanings as above).

[0010] Formula [I] where —Q— is —Ar— represents a polymer that containsin the backbone a 9-oxo-9-phosphafluorene-2,7-diyl skeleton and anarylene skeleton of the following general formula [IV]:

[0011] (wherein Ar and n have the same meanings as above).

[0012] Formula [I] where —Q— is a vinylene group of formula [II]represents a polymer that contains in the backbone a9-oxo-9-phosphafluorene-2,7-diyl skeleton and a vinylene skeleton of thefollowing general formula [V]:

[0013] (wherein R, R′ and n have the same meanings as above).

[0014] In formulae [I], [III], [IV] and [V], R represents a hydrogenatom, or an optionally-substituted alkyl, cycloalkyl, aralkyl, aryl,alkoxy, cycloalkyloxy, aralkyloxy or aryloxy group.

[0015] The alkyl group of the optionally-substituted alkyl group for Rmay be a linear or branched alkyl group preferably having from 1 to 20,more preferably from 1 to 15 carbon atoms. Its examples are methyl,ethyl, n- or iso-propyl, n-, iso- sec- or tert-butyl, n-, iso-, sec-,tert- or neo-pentyl, n-hexyl, n-heptyl, n-octyl, 2-octyl and n-nonylgroups.

[0016] The cycloalkyl group of the optionally-substituted cycloalkylgroup for R preferably has from 5 to 18, more preferably from 5 to 10carbon atoms. Its examples are cyclopentyl, cyclohexyl, cyclooctyl andcyclododecyl groups.

[0017] The aralkyl group of the optionally-substituted aralkyl group forR preferably has from 7 to 13, more preferably from 7 to 11 carbonatoms. Its examples are benzyl, phenethyl and naphthylmethyl groups.

[0018] The aryl group of the optionally-substituted aryl group for Rpreferably has from 6 to 18, more preferably from 6 to 14 carbon atoms.Its examples are phenyl, naphthyl, tolyl and xylyl groups.

[0019] The alkoxy group of the optionally-substituted alkoxy group for Rpreferably has from 1 to 20, more preferably from 1 to 15 carbon atoms.Its examples are methoxy, ethoxy, n- or iso-propoxy, n-, iso-, sec- ortert-butoxy, n-, iso-, sec-, tert- or neo-pentyloxy, n-hexyloxy,n-heptyloxy, n-octyloxy and 2-octyloxy groups.

[0020] The cycloalkyloxy group of the optionally-substitutedcycloalkyloxy group for R preferably has from 5 to 18, more preferablyfrom 5 to 10 carbon atoms. Its examples are cyclopentyloxy,cyclohexyloxy, cyclooctyloxy and cyclododecyloxy groups.

[0021] The aralkyloxy group of the optionally-substituted aralkyloxygroup for R preferably has from 7 to 13, more preferably from 7 to 11carbon atoms. Its examples are benzyloxy, phenethyloxy andnaphthylmethyloxy groups.

[0022] The aryloxy group of the optionally-substituted aryloxy group forR preferably has from 6 to 18, more preferably from 6 to 14 carbonatoms. Its examples are phenoxy, 1- or 2-naphthyloxy, tolyloxy andxylyloxy groups.

[0023] The substituent for these alkyl, cycloalkyl, aralkyl, aryl,alkoxy, cycloalkyloxy, aralkyloxy and aryloxy groups includes, forexample, an alkyl group such as methyl, ethyl, n- or iso-propyl; analkoxy group such as methoxy, ethoxy; and a halogen atom such asfluorine, chlorine, bromine, iodine. Except these, any other substituentnot interfering with the polycondensation in the process of producingthe polymer of the invention is acceptable for these groups.

[0024] In formula [IV], Ar represents a substituted or unsubstitutedarylene group, of which the arylene group has from 6 to 14 carbon atoms.Concretely, it includes 1,4-phenylene, 2-methyl-1,4-phenylene,2,5-dimethyl-1,4-phenylene, 2,3-dimethyl-1,4-phenylene,2,3,5,6-tetramethyl-1,4-phenylene, 2,5-dimethoxy-1,4-phenylene,2,5-dihexyloxy-1,4-phenylene and2,5-bis(1-methylheptyloxy)-1,4-phenylene groups.

[0025] In formulae [II] and [V], R′ is a hydrogen atom, anoptionally-substituted alkyl, cycloalkyl, aryl or aralkyl group, a cyanogroup, or an alkoxycarbonyl group.

[0026] For the definitions and the examples of the alkyl, cycloalkyl,aryl or aralkyl group of the optionally-substituted alkyl, cycloalkyl,aryl or aralkyl for R′, and also for the definitions and the examples ofthe substituents for these groups, referred to are the same as thosementioned hereinabove for R respectively.

[0027] The alkoxycarbonyl group for R′ is preferably one containing analkoxy group having from 1 to 20, more preferably from 1 to 15 carbonatoms. Its examples are methoxycarbonyl, ethoxycarbonyl, n- oriso-propoxycarbonyl, n-, iso-, sec- or tert-butoxycarbonyl, n-, iso-,sec-, tert- or neo-pentoxycarbonyl, n-hexoxycarbonyl, n-heptoxycarbonyl,n-octoxycarbonyl and 2-octoxycarbonyl groups.

[0028] R′ may bond to any carbon of the olefin site of the formula.

[0029] The polymer of formula [III] may be produced throughdehalo-polycondensation of a 2,7-dihalo-9-oxo-9-phosphafluorene of thefollowing general formula [VI]:

[0030] (wherein R has the same meaning as above, and X represents ahalogen atom).

[0031] Examples of the halogen atom for X in formula [VI] are chlorine,bromine and iodine atoms.

[0032] The polycondensation effectively goes on in the presence of atransition metal-based chemical substance, especially a low-valancetransition metal-based chemical substance that is active to organichalogen compounds in a reaction mode generally known as oxidativeaddition reaction. The transition metal is preferably a latter-periodtransition metal of Groups 8 to 10 of the Periodic Table. Concretely, itincludes, for example, iron, ruthenium, cobalt, rhodium, iridium,nickel, palladium and platinum. Especially preferred is nickel. Thelow-valence transition metal-based chemical substance may be previouslyprepared, or may be prepared in situ by adding a reducing agent to ahigher-valence transition metal-based chemical substance and may bedirectly used in the reaction as it is. The reducing agent includes, forexample, sodium borohydride, lithiumaluminium hydride, metal zinc, andhydrazine. Preferably, the amount of the transition metal-based chemicalsubstance to be used is at least 1 equivalent to the2,7-dihalo-9-oxo-9-phosphafluorene. However, when the reaction iseffected in the presence of such a reducing agent, using even acatalytic amount of the compound may attain the intended object.

[0033] The polycondensation may be effected at various temperatures, butis generally effected at a temperature falling between −70 and 180° C.,preferably between 0 and 150° C.

[0034] Preferably, the polycondensation is effected in a solvent. Thesolvent includes, for example, N,N-dimethylformamide,hexamethylphosphoryl triamide, toluene, benzene, and tetrahydrofuran.The amount of the solvent to be used in effecting the polycondensationis not specifically defined but falls generally between 0.1 and 100 mL,preferably between 1 and 20 mL relative to 1 mmol of the starting2,7-dihalo-9-oxo-9-phosphafluorene.

[0035] After the reaction, the reaction mixture may be post-treatedthrough per-se known extrusion crystallization, filtration or washingwith water, and the reaction product may be readily isolated andpurified through reprecipitation or the like.

[0036] The polymer of formula [IV] may be produced by dissolving the2,7-dihalo-9-oxo-9-phosphafluorene of formula [VI] in a solvent followedby polycondensing it with an arylenebisboronic acid of the followinggeneral formula [VII]:

(HO)₂B—Ar—B(OH)₂  [VII]

[0037] (wherein Ar has the same meaning as above).

[0038] Preferred examples of the arylenebisboronic acid are1,2-phenylenebisboronic acid, 1,3-phenylenebisboronic acid,1,4-phenylenebisboroic acid, 2-methyl-1,4-phenylenebisboronic acid,2,5-dimethyl-1,4-phenylenebisboronic acid,2,3-dimethyl-1,4-phenylenebisboronic acid,1,4-dimethyl-2,3-phenylenebisboronic acid,2,3,5,6-tetramethyl-1,4-phenylenebisboronic acid,2,5-dimethoxy-1,4-phenylenebisboronic acid,2,5-dihexyloxy-1,4-phenylenebisboronic acid, and2,5-bis(1-methylheptyloxy)-1,4-phenylenediboronic acid.

[0039] The amount of the arylenebisboronic acid to be used for thepolycondensation may fall between 0.5 and 2 equivalents, preferablybetween 0.7 and 1.2 equivalents relative to one equivalent of the2,7-dihalo-9-oxo-9-phosphafluorene to be reacted with it.

[0040] The polycondensation rapidly goes on at a preferred rate in thepresence of a palladium catalyst. Various known types of palladiumcatalyst may be employed, but preferred are low-valence complexes.Especially preferred are 2-valent complexes with a ligand of a tertiaryphosphine or tertiary phosphite. Also preferred is an embodiment ofusing a suitable precursor that may be readily converted into such alow-valence complex in the reaction system.

[0041] Still also preferred is an embodiment that comprises mixing acomplex not having a tertiary phosphine or phosphite as a ligand with atertiary phosphine or phosphite to thereby form a low-valence complexhaving such a ligand of a tertiary phosphine or phosphite in thereaction system. Various types of tertiary phosphines and tertiaryphosphites are useful for the ligand of good potency in any of thesemethods.

[0042] Preferred examples of the ligand for use in the reaction aretriphenyl phosphine, diphenylmethyl phosphine, phenyldimethyl phosphine,1,4-bis(diphenylphosphino)butane, 1,3-bis(diphenylphosphino)propane,1,1′-bis(diphenylphosphino)ferrocene, trimethyl phosphite, and triphenylphosphite. Complexes with no ligand of a tertiary phosphine or tertiaryphosphite, which is used herein as combined or not combined with any ofthe above-mentioned ligands include, but not limited to,bis(dibenzylideneacetone)palladium, palladium acetate,dichlorobis(benzonitrile)palladium,dichloro(1,5-cyclooctadiene)palladium(II), palladium(II)bishexafluoropentanedionate, and palladium(II) bispentanedionate.Preferred examples of phosphine or phosphite complexes for use hereinare dimethylbis(triphenylphosphine)palladium,dimethylbis(diphenylmethylphosphine)palladium,dimethylbis(dimethylphenylphosphine)palladium,dimethylbis(triethylphosphine)palladium,(ethylene)bis(triphenylphosphine)palladium,tetrakis(triphenylphosphine)palladium,bis(tricyclohexylphosphine)palladium, anddichlorobis(triphenylphosphine)palladium.

[0043] The amount of the palladium complex to be used herein fallsbetween 0.00001 and 20 equivalents, preferably between 0.0001 and 2equivalents relative to one equivalent of the starting2,7-dihalo-9-oxo-9-phosphafluorenone.

[0044] Preferably, the coupling reaction with the palladium complex ispromoted by a base. For it, various types of inorganic or organic basesmay be used. Their examples are lithium carbonate, sodium carbonate,potassium carbonate, lithium hydroxide, sodium hydroxide, potassiumhydroxide, lithium oxide, sodium acetate, potassium acetate, magnesiumoxide, calcium oxide, barium hydroxide, trilithium phosphate, trisodiumphosphate, tripotassium phosphate, cesium fluoride, cesium carbonate,aluminium oxide, trimethylamine, triethylamine,N,N,N′,N′-tetramethylethylenediamine, diisopropylamine,diisopropylethylamine, N-methylpiperidine,2,2,6,6-tetramethyl-N-methylpiperidine, pyridine,4-dimethylaminopyridine, N-methylmorpholine, sodium ethoxide, andpotassium tert-butoxide. The amount of the base to be used falls between1 and 100 equivalents, preferably between 2 and 20 equivalents, relativeto one equivalent of the starting 2,7-dihalo-9-oxo-9-phosphafluorene.

[0045] The reaction may be effected at various temperatures, but isgenerally effected at a temperature falling between −70 and 180° C.,preferably between 0 and 150° C.

[0046] Preferably, the reaction is effected in a solvent. Examples ofthe solvent are N,N-dimethylformamide, hexamethylphosphoryl triamide,toluene, benzene, chloroform, tetrahydrofuran and water. For promotingthe polycondensation, the amount of the solvent to be used is notspecifically defined, but generally falls between 0.1 and 100 mL,preferably between 1 and 20 mL, relative to 1 mmol of the starting2,7-dihalo-9-oxo-9-phosphafluorene.

[0047] After the reaction, the reaction mixture may be post-treatedthrough per-se known extrusion crystallization, filtration or washingwith water, and the reaction product may be readily isolated andpurified through reprecipitation or the like.

[0048] The polymer of formula [V] may be produced throughpolycondensation, known as Heck reaction, of the2,7-dihalo-9-oxo-9-phosphafluorene of formula [VI] with an olefin of thefollowing general formula [VIII]:

[0049] (wherein R′ has the same meaning as above).

[0050] The polycondensation efficiently goes on in the presence of atransition metal-based chemical substance, especially that generallyused in Heck reaction. The transition metal is preferably alatter-period transition metal of Groups 8 to 10 of the Periodic Table.More effective are low-valence transition metal-based chemicalsubstances, especially those including nickel and palladium. Thelow-valence transition metal-based chemical substances for use hereinmay be previously prepared ones. Apart from it, also preferred isanother embodiment of using a suitable precursor capable of beingreadily converted into a low-valence transition metal-based chemicalsubstance in the reaction system. The transition metal-based chemicalsubstances that are used in the invention in any embodiment of using thepreviously-prepared one or using a precursor of the compound are, forexample, simple substances of metal such as metal powder; metals carriedby activated charcoal or the like; and metal salts or metal complexeswith various types of ligand. Preferred for use herein are complexeswith a ligand of tertiary phosphines, tertiary phosphites, imines orpyridine derivatives, as well as other chemical compounds prepared byadding any of these ligands to the above-mentioned metals of latterperiod of the Periodic Table.

[0051] Preferred examples of the ligand for use in the reaction aretriphenyl phosphine, diphenylmethyl phosphine, phenyldimethyl phosphine,tri(2-furyl) phosphine, 1,4-bis(diphenylphosphino)butane,1,3-bis(diphenylphosphino)propane, 1,1′-bis(diphenylphosphino)ferrocene,trimethyl phosphite, triphenyl phosphite, dimethyl phenylphosphonous,dimethyl methylphosphinous, ethylene-1,2-bisoxazoline,diphenylphosphinomethyloxazoline, pyridine, 1,1′-dipyridyl, andorthophenanthroline.

[0052] Preferred examples of the transition metal compound, which isused in the invention as a previously-prepared one or in the form of itsprecursor, include, but are not limited to, palladium powder, activatedcharcoal-carried palladium, bis(dibenzylideneacetone)palladium,palladium chloride, palladium acetate,dichlorobis(benzonitrile)palladium,dichloro(1,5-cyclooctadiene)palladium(II), palladium(II)bishexafluoropentanedionate, palladium(II) bispentanedionate,dimethylbis(triphenylphosphine)palladium,dimethylbis(diphenylmethylphosphine)palladium,dimethylbis(dimethylphenylphosphine)palladium,dimethylbis(triethylphosphine)palladium,dimethyl[1,1′-bis(diphenylphosphino)ferrocene]palladium,dimethyl[1,4-bis(diphenylphosphino)butane]palladium,(ethylene)bis(triphenylphosphine)palladium,tetrakis(triphenylphosphine)palladium,bis(tricyclohexylphosphine)palladium,dichlorobis(triphenylphosphine)palladium,dichloro(orthophenanthroline)palladium,dichloro[ethylene-1,2-bisoxazoline]palladium, anddichlorobis(triphenylphosphine)nickel.

[0053] The amount of the transition metal-based chemical substance to beused herein falls between 0.00001 and 20 equivalents, preferably between0.0001 and 2 equivalents relative to one equivalent of the starting2,7-dihalo-9-oxo-9-phosphafluorene.

[0054] Preferably, the reaction is promoted by a base. For it, varioustypes of inorganic or organic bases may be used. Their examples arelithium carbonate, sodium carbonate, potassium carbonate, sodiumacetate, potassium acetate, magnesium oxide, calcium oxide,trimethylamine, triethylamine, tributylamine,N,N,N′,N′-tetramethylethylenediamine, diisopropylamine,diisopropylethylamine, dicyclohexylmethylamine, N-methylpiperidine,2,2,6,6-tetramethyl-N-methylpiperidine, pyridine,4-dimethylaminopyridine, and N-methylmorpholine. The amount of the baseto be used may be far excessive over the reactants, but generally fallsbetween 1 and 100 equivalents, preferably between 2 and 20 equivalentsrelative to the starting 2,7-dihalo-9-oxo-9-phosphafluorene.

[0055] The amount of the olefin to be used for starting the reaction isnot specifically defined, but, in general, it is preferably at least 0.5equivalents, more preferably from 0.95 to 200 equivalents relative to2,7-dihalo-9-oxo-9-phosphafluoene for realizing a higher degree ofpolymerization. When the olefin is gaseous at room temperature, itspressure shall be determined depending on the solubility and thereactivity of the gaseous olefin, but in general, it may fall between0.1 and 100 atmospheres, preferably between 0.5 and 10 atmospheres.

[0056] The reaction may be effected at various temperatures, but isgenerally effected at a temperature falling between −70 and 180° C.,preferably between 0 and 150° C.

[0057] Preferably, the reaction is effected in a solvent. Examples ofthe solvent are N,N-dimethylformamide, hexamethylphosphoryl triamide,xylene, toluene, benzene, tetrahydrofuran, and dibutyl ether. Forpromoting the polycondensation, the amount of the solvent to be used isnot specifically defined, but generally falls between 0.1 and 100 mL,preferably between 0.3 and 10 mL relative to 1 mmol of the starting2,7-dihalo-9-oxo-9-phosphafluorene. When the base used herein is liquid,its amount may be far excessive over the reactants so that the excessliquid base may serve as a solvent for the reaction. This is alsoanother preferred embodiment of the invention.

[0058] After the reaction, the reaction mixture may be post-treatedthrough per-se known extrusion crystallization, filtration or washingwith water, and the reaction product may be readily isolated andpurified through reprecipitation or the like.

[0059] The starting compound, 2,7-dihalo-9-oxo-9-phosphafluoene compoundin the production method of the invention is obtained by halogenating a9-oxo-9-phosphafluorene of the following general formula [IX]

[0060] (wherein R has the same meaning as above), with a halogenmolecule.

[0061] For the reaction, preferably used is molecular chlorine, bromineor iodine. The amount of the halogen molecule to be used must be atleast 2 equivalents relative to the 9-oxo-9-phosphafluorene of formula[IX], but may be excess over it.

[0062] The reaction effectively goes on in the presence of a Lewis acidcatalyst. The Lewis acid catalyst may be any one generally used inaromatic electrophilic substitution. Concretely, it includes, forexample, aluminium chloride, aluminium bromide, iron chloride, andantimony chloride. Metals that are the precursors for them may also beused, including, for example, metal aluminium and metal iron. The amountof the catalyst to be used may be at least one equivalent relative tothe starting 9-oxo-9-phosphafluorene of formula [IX], but may be acatalytic amount thereof for efficient reaction.

[0063] The reaction may be effected at various temperatures, but isgenerally effected at a temperature falling between −70 and 180° C.,preferably between 0 and 150° C.

[0064] No solvent may be used in the reaction. However, when thestarting 9-oxo-9-phosphafluorene is solid, it may be dissolved in asolvent. For the solvent, for example, preferred arehalogenohydrocarbons; carboxylic acids such as acetic acid; carbondisulfide; and aromatic nitro compounds such as nitrobenzene.

[0065] The product may be readily isolated and purified in any ordinarymanner, for example, through recrystallization or chromatography.

[0066] 2,7-Dihalo-9-oxo-9-phosphafluorene compounds of formula [VI] arenovel compounds, not disclosed in any literature.

[0067] The polymer of the invention can be formed into thin films in anysimple working technique of, for example, spin coating or casting, andit is useful as a component of organic thin-film electrochromic elementsand organic luminescent elements.

[0068] The invention is described more concretely with reference to thefollowing Examples, which, however, are not intended to restrict thescope of the invention.

EXAMPLES Example 1

[0069] In a nitrogen atmosphere, 0.336 g (1.2 mmols) ofbis(1,5-cyclooctadiene)nickel, 0.2 mL of 1,5-cyclooctadiene, 0.200 g(1.3 mmols) of α,α′-dipyridyl, and 0.484 g (1.0 mmol) of2,7-dibromo-9-nonyl-9-oxo-9-phosphafluorene (of formula [VI] where R isn-nonyl group and X is bromine) were added to 20 mL ofN,N-dimethylformamide, and stirred under heat at 60° C. for 48 hours.The reaction mixture was poured into 100 mL of 0.5 M dilutedhydrochloric acid, and the resulting powder was taken out throughfiltration. The powder was washed with 50 mL of water, then dissolved in5 mL of chloroform, and reprecipitated in 100 mL of methanol to therebyisolate 0.295 g (0.91 mmols in terms of the monomer unit) of a polymerhaving repeating units of a 9-nonyl-9-oxo-9-phosphafluorene-2,7-diylgroup (of formula [III] where R is nonyl group). Thus obtained, thepolymer is a novel compound not disclosed in any literature. Calculatedthrough gel permeation chromatography (GPC method), its number-averagemolecular weight was 3980 and its weight-average molecular weight was8025.

[0070] Its NMR spectral data and elementary analysis data are mentionedbelow.

[0071]¹H-NMR(CDCl₃):δ0.83(3H,brs),1.22(10H,brs),1.37(2H,brs),1.61(2H,brs),2.17(2H,brs),7.87(4H,brs),8.09(2H,brs).

[0072]³¹P-NMR(CDCl₃): δ43.7.

[0073] Elementary Analysis: Calculated as n=12 (C₂₅₂H₃₀₁O₁₂P₁₂Br): C,76.17; H, 7.63; Br, 2.01.

[0074] Found: C, 75.93; H, 7.88; Br, 2.22.

Example 2

[0075] In the same manner as in Example 1, obtained was 0.251 g (0.81mmols in terms of the monomer unit) of a polymer having repeating unitsof a 9-(2-octyl)-9-oxo-9-phosphafluorene-2,7-diyl group (of formula[III] where R is 2-octyl group), for which, however, used was 0.470 g(1.0 mmol) of 2,7-dibromo-9-(2-octyl)-9-oxo-9-phosphafluoene (of formula[VI] where R is 2-octyl group and X is bromine) in place of2,7-dibromo-9-nonyl-9-oxo-9-phosphafluoene in Example 1. Thus obtained,the polymer is a novel compound not disclosed in any literature.Calculated through gel permeation chromatography method (GPC) method,its number-average molecular weight was 3356 and its weight-averagemolecular weight was 4679.

[0076] Its NMR spectral data and elementary analysis data are mentionedbelow.

[0077]¹H-NMR(CDCl₃):δ0.84(3H,brs),1.24(9H,brs),1.50(1H,brs),1.72(2H,brs),1.92(1H,brs),2.34(1H,brs),7.85(4H,brs),8.05(2H,brs).

[0078]³¹P-NMR(CDCl₃): δ50.2.

[0079] Elementary Analysis: Calculated as n=10 (C₂₀₀H₂₃₁O₁₀P₁₀Br): C,75.43; H, 7.31; Br, 2.51.

[0080] Found: C, 75.23; H, 7.45; Br, 2.54.

Example 3

[0081] In the same manner as in Example 1, obtained was 0.99 g (0.38mmols in terms of the monomer unit) of a polymer having repeating unitsof a 9-propyl-9-oxo-9-phosphafluorene-2,7-diyl group (of formula [III]where R is n-propyl group), for which, however, used was 0.200 g (0.50mmol) of 2,7-dibromo-9-propyl-9-oxo-9-phosphafluoene (of formula [VI]where R is n-propyl group and X is bromine) in place of2,7-dibromo-9-nonyl-9-oxo-9-phosphafluoene in Example 1, and used were0.168 g (0.50 mmol) of bis(1,5-cyclooctadiene)nickel, 0.1 mL of1.5-cyclooctadiene, 0.100 g (0.64 mmol) of α,α′-dipyridyl and 10 mL ofN,N-dimethylformamide. Thus obtained, the polymer is a novel compoundnot disclosed in any literature. Its IR spectrometry confirmed that thepolymer is a hydrate. The number-average molecular weight of the polymercalculated through elementary analysis was 3180.

[0082] The NMR spectral data and elementary analysis data of the polymerare mentioned below.

[0083]¹H-NMR(CDCl₃):δ1.03(3H,brs),1.64(2H,brs),1.95(2H,brs),2.18(2H,brs),7.74(4H,brs),8.04(2H,brs).

[0084]³¹P-NMR(CDCl₃): δ43.5.

[0085] Elementary Analysis: Calculated as n=12 (C₁₈₀H₁₈₁O₂₄P₁₂Br): C,67.99; H, 5.74.

[0086] Found: C, 68.05; H, 5.72.

Example 4

[0087] In a nitrogen atmosphere, a mixture of 0.012 g (0.010 mmol) oftetrakis(triphenylphosphine)palladium (0), 0.484 g (1.0 mmol) of2,7-dibromo-9-nonyl-9-oxo-9-phosphafluorene (of formula [VI] where R isn-nonyl group and X is bromine), 0.367 g (1.0 mmol) of2,5-dihexyloxy-1,4-phenylenediboronic acid, 2.0 g of tripotassiumphosphate and 10 mL of N,N-dimethylformamide was heated at 125° C., andstirred for 48 hours at the temperature. The reaction mixture was pouredinto 100 mL of water, and the resulting powder was taken out throughfiltration. The powder was washed with 50 mL of water, then dissolved in5 mL of chloroform, and reprecipitated in 100 mL of methanol to therebyisolate 0.495 g (0.83 mmols in terms of the monomer unit) of a polymerhaving in the backbone a 9-nonyl-9-oxo-9-phosphafluorene-2,7-diyl groupand a 2,5-dihexyloxy-1,4-phenylene group (of formula [IV] where R isnonyl group and Ar is 2,5-dihexyloxy-1,4-phenylene group). Thusobtained, the polymer is a novel compound not disclosed in anyliterature. Calculated through gel permeation chromatography method (GPCmethod), its number-average molecular weight was 10100 and itsweight-average molecular weight was 22000. Calculated through elementaryanalysis, its mean molecular weight was 8290. Its NMR spectral data andelementary analysis data are mentioned below.

[0088]¹H-NMR(CDCl₃):δ0.86(6H,brs),1.31(16H,brs),1.64(12H,brs),1.77(2H,brs),4.02(4H,brs),7.10(2H,m),7.84-7.87(2H,m),7.83-7.93(2H,m),8.09(2H,d,J=9.3 Hz).

[0089]³¹P-NMR(CDCl₃): δ43.9.

[0090] Elementary Analysis: Calculated as n=13 (C₅₂₈H₇₁₄O₄₀P₁₄Br₂): C,76.45; H, 8.68; Br, 1.93.

[0091] Found: C, 76.61; H, 8.83; Br, 2.20.

Example 5

[0092] In the same manner as in Example 4, obtained was 0.460 g (0.89mmols in terms of the monomer unit) of a polymer having in the backbonea 9-oxo-9-phosphor-9-propylfluorene-2,7-diyl group and a2,5-dihexyloxy-1,4-phenylene group (of formula [IV] where R is propylgroup and Ar is 2,5-dihexyloxy-1,4-phenylene group), for which, however,used was 0.400 g (1.0 mmol) of2,7-dibromo-9-oxo-9-phosphor-9-propylfluorene (of formula [VI] where Ris n-propyl group and X is bromine) in place of2,7-dibromo-9-nonyl-9-oxo-9-phosphafluorene. Thus obtained, the polymeris a novel compound not disclosed in any literature. Calculated throughGPC method, the number-average molecular weight of the THF-soluble partof the polymer was 6230 and the weight-average molecular weight thereofwas 8980. Calculated through elementary analysis, the mean molecularweight of the polymer was 9090.

[0093] The NMR spectral data and elementary analysis data of the polymerare mentioned below.

[0094]¹H-NMR(CDCl₃):δ0.87(6H,brs),0.99(3H,brs),1.31(2H,brs),1.77(6H,brs),2.13(2H,brs,),3.98(4H,brs),6.98(2H,s),7.87(4H,m),8.09(2H,d,J=8.0 Hz).

[0095]³¹P-NMR(CDCl₃): δ44.0.

[0096] Elementary Analysis: Calculated as n=14 (C₄₇₇H₅₈₇O₄₃P₁₅Br₂): C,74.94; H, 7.73; Br, 2.10.

[0097] Found: C, 74.73; H, 7.88; Br, 1.76.

Example 6

[0098] In the same manner as in Example 4, obtained was 0.319 g (0.80mmol in terms of the monomer unit) of a polymer having in the backbone a9-nonyl-9-oxo-9-phosphafluorene-2,7-diyl group and a 1,4-phenylene group(of formula [IV] where R is nonyl group and Ar is 1,4-phenylene group),for which, however, used was 0.166 g (1.0 mmol) of1,4-phenylenediboronic acid in place of2.5-dihexyloxy-1,4-phenylenediboronic acid. Thus obtained, the polymeris a novel compound not disclosed in any literature. Calculated throughGPC method, the number-average molecular weight of the THF-soluble partof the polymer was 2110 and the weight-average molecular weight thereofwas 2380. Calculated through elementary analysis, the mean molecularweight of the polymer was 4090. The NMR spectral data and elementaryanalysis data of the polymer are mentioned below.

[0099]¹H-NMR(CDCl₃):δ0.83(3H,brs),1.20(10H,brs),1.61(2H,brs),2.15(2H,brs),7.47(2H,m),7.65-7.87(6H,m),8.14(2H,m).

[0100]³¹P-NMR(CDCl₃): δ43.9.

[0101] Elementary Analysis: Calculated as n=9 (C₂₆₄H₂₈₆O₁₀P₁₀Br₂): C,77.55; H, 7.05; Br, 3.91.

[0102] Found: C, 77.37; H, 7.10; Br, 3.98.

Example 7

[0103] 0.0012 g (0.010 mmol) of palladium acetate, 0.0061 g (0.020 mmol)of tri-o-tolylphosphine, 0.43 mL of tri-n-butylamine, 0.235 g (0.50mmol) of 2,7-dibromo-9-(2-octyl)-9-oxo-9-phosphafluorene (of formula[VI] where R is 2-octyl group and X is bromine) and 0.5 mL ofN,N-dimethylformamide were put into a glass reactor. The reaction systemwas connected to a normal-pressure ethylene reactor, via which it wascharged with ethylene. Then, the glass reactor was dipped in an oil bathat 125° C. and its contents were stirred under heat for 48 hours. Thereaction mixture was poured into 100 mL of 0.5 M diluted hydrochloricacid, and the resulting powder was taken out through filtration. Thepowder was washed with 50 mL of water, then dissolved in 5 mL ofchloroform, and reprecipitated in 100 mL of diethyl ether to therebyisolate 0.077 g (0.23 mmol in terms of the monomer unit) of a polymerhaving repeating units of a 9-(2-octyl)-9-oxo-9-phosphafluoene-2,7-diylgroup and a vinylene group (of formula [V] where R is 2-octyl group).Thus obtained, the polymer is a novel compound not disclosed in anyliterature. Calculated through gel permeation chromatography, thenumber-average molecular weight of the polymer was 1530 and theweight-average molecular weight thereof was 2540.

[0104] The NMR spectral data and elementary analysis data of the polymerare mentioned below.

[0105]¹H-NMR(CDCl₃):δ0.84(6H,brs),1.03(2H,brs),1.23(6H,brs),1.47(1H,brs),1.86(1H,brs),2.28(1H,brs),6.94-8.46(8H,m).

[0106]³¹P-NMR(CDCl₃): δ50.4.

[0107] Elementary Analysis: Calculated as n=5 (C₁₃₀H₁₄₈O₆P₆Br₂): C,72.55; H, 6.93.

[0108] Found: C, 72.15; H, 7.27.

Example 8

[0109] In the same manner as in Example 7, obtained was 0.112 g (0.39mmol in terms of the monomer unit) of a polymer having repeating unitsof a 9-propyl-9-oxo-9-phosphafluorene-2,7-diyl group and a vinylenegroup (of formula [V] where R is n-propyl group), for which, however,used was 0.200 g (0.50 mmol) of2,7-dibromo-9-propyl-9-oxo-9-phosphafluorene (of formula [VI] where R isn-propyl group and X is bromine) in place of2,7-dibromo-9-(2-octyl)-9-oxo-9-phosphafluorene in Example 7. Thusobtained, the polymer is a novel compound not disclosed in anyliterature. Its IR absorptiometry confirmed that the polymer is ahydrate. Calculated through elementary analysis, the number-averagemolecular weight of the polymer was 2410.

[0110] The NMR spectral data and elementary analysis data of the polymerare mentioned below.

[0111]¹H-NMR(CDCl₃):δ0.99(3H,brs),1.35(2H,brs),1.76(2H,brs),2.14(2H,m),7.23(2H,s),7.43-8.04(6H,m).

[0112]³¹P-NMR(CDCl₃): δ43.6.

[0113] Elementary Analysis: Calculated as n=7 (C₁₃₄H₁₃₄O₁₆P₈Br₂): C,66.84; H, 5.61.

[0114] Found: C, 66.96; H, 6.05.

Example 9

[0115] In the same manner as in Example 7, obtained was 0.114 g (0.40mmol in terms of the monomer unit) of a polymer having repeating unitsof a 9-propyl-9-oxo-9-phosphafluorene-2,7-diyl group and a vinylenegroup (of formula [V] where R is n-propyl group), for which, however,used was xylene in place of N,N-dimethylformamide in Example 8. Thusobtained, the polymer is a novel compound not disclosed in anyliterature. Its IR absorptiometry confirmed that the polymer is ahydrate. Calculated through elementary analysis, the number-averagemolecular weight of the polymer was 3260.

[0116] The NMR spectral data and elementary analysis data of the polymerare mentioned below.

[0117]¹H-NMR(CDCl₃):δ0.98(3H,brs),1.37(2H,brs),1.97(2H,brs),2.14(2H,m),7.20(2H,s),7.57-8.16(6H,m).

[0118]³¹P-NMR(CDCl₃): δ43.4.

[0119] Elementary Analysis: Calculated as n=10 (C₁₈₅H₁₈₅O₂₂P₁₁Br₂): C,68.14; H, 5.72.

[0120] Found: C, 68.04; H, 6.12.

Example 10

[0121] 12.3 mL of bromine was added to a mixture 5.88 g (24.3 mmol) of9-oxo-9-phospha-9-propylfluorene (of formula [IX] where R is n-propylgroup) and 0.243 g (4.35 mmol) of iron powder within a period of 30minutes, and stirred under heat at 65° C. for 24 hours. The reactionmixture was mixed with 500 mL of water, and extracted with 500 mL ofchloroform. The resulting chloroform extract was washed with 200 mL ofsaturated sodium thiosulfate. Then, this was dried with magnesiumsulfate anhydride, and concentrated, and the resulting solid wasrecrystallized from methanol to thereby isolate 6.32 g (15.8 mmol) of2,7-dibromo-9-oxo-9-phospha-9-propylfluorene (of formula [VI] where R isn-propyl group). Thus obtained, the compound was a colorless tabularcrystal, and is a novel compound not disclosed in any literature. Its IRand NMR spectral data, melting point and elementary analysis data arementioned below.

[0122] IR(KBr):2956.3,2933.2,2875.3,1456.0,1394.3,1174.4,1072.2,81 7.7cm⁻¹.

[0123]¹H-NMR(CDCl₃): δ1.00(3H,t,J=7.3Hz),1.50-1.59(2H,m),2.04-2.14(2H,m), 7.61(2H,dd,J=1.9,8.3Hz),7.71(2H,dd,J=0.6,8.3 Hz),7.92(2H,dd,J=1.6,9.2 Hz).

[0124]¹³C-NMR(CDCl₃): δ15.5(d,J=16.8 Hz),15.9(d,J=3.5 Hz),32.3(d,J=69.7Hz), 122.8(d,J=10.1 Hz),123.6(d,J=13.7 Hz),132.4(d,J=10.3Hz),134.0(d,J=98.4 Hz), 136.3(d,J=1.9 Hz),139.0(d,J=9.98 Hz).

[0125]³¹P-NMR(CDCl₃): δ42.2.

[0126] m.p.: 226.0-226.4° C.

[0127] Elementary Analysis: Calculated as C₁₅H₁₃OPBr₂: C, 45.04; H,3.28.

[0128] Found: C, 45.08; H, 3.10.

Example 11

[0129] In the same manner as in Example 9, obtained was 5.63 g (11.6mmol) of 2,7-dibromo-9-nonyl-9-oxo-9-phosphafluoene (of formula [VI]where R is nonyl groups), for which, however, used was 7.93 g (24.3mmol) of 9-nonyl-9-oxo-9-phosphafluorene (of formula [IX] where R isnonyl groups) in place of 9-oxo-9-phospha-9-propylfluorene in Example10. Thus obtained, the compound was a colorless acicular crystal, and isa novel compound not disclosed in any literature.

[0130] Its IR and NMR spectral data, melting point and elementaryanalysis data are mentioned below.

[0131] IR(KBr):2952.5,2921.6,2850.7,1454.1,1394.3,1176.4,1089.6,821.5cm⁻¹.

[0132]¹H-NMR(CDCl₃): δ0.86(3H,t,J=6.7Hz),1.21-1.27(10H,m),1.28-1.33(2H,m),1.47-1.53(2H,m),2.03-2.13(2H,m),7.61(2H,dd,J=2.3,8.0Hz),7.70(2H,dd,J=0.6,8.0 Hz), 7.92(2H,dd,J=1.5,9.2 Hz).

[0133]¹³C-NMR(CDCl₃): δ14.1,21.9(d,J=18.9Hz),22.6,28.9,29.2,29.3,30.0(d,J=69.8 Hz), 30.8(d,J=15.5Hz),31.8,122.8(d,J=10.1 Hz),123.7(d,J=13.6 Hz),132.4(d,J=10.3 Hz),134.0(d,J=98.6 Hz),136.5(d,J=1.8 Hz),139.0(d,J=19.5 Hz).

[0134]³¹P-NMR(CDCl₃): δ42.5.

[0135] m.p.: 95.0-96.0° C.

[0136] Elementary Analysis: Calculated as C₂₁H₂₅OPBr₂: C, 52.09; H,5.20.

[0137] Found: C, 52.21; H, 5.11.

Example 12

[0138] In the same manner as in Example 10, obtained was 5.35 g (11.4mmol) of 2,7-dibromo-9-(2-octyl)-9-oxo-9-phosphafluoene (of formula [VI]where R is 2-octyl group), for which, however, used was 7.59 g (24.3mmol) of 9-(2-octyl)-9-oxo-9-phosphafluorene (of formula [IX] where R is2-octyl group) in place of 9-oxo-9-phospha-9-propylfluorene in Example10. Thus obtained, the compound was a colorless acicular crystal, and isa novel compound not disclosed in any literature.

[0139] Its IR and NMR spectral data, melting point and elementaryanalysis data are mentioned below.

[0140] IR(KBr):2950.6,2925.5,2854.1,1450.2,1392.4,1172.5,1085.7,821.5cm⁻¹.

[0141]¹H-NMR(CDCl₃): δ0.84(3H,t,J=6.0 Hz),1.00(3H,dd,J=6.9,18.9 Hz),1.21(8H,brs),1.43-1.46(1H,m),1.74-1.80(1H,m),2.19-2.24(1H,m),7.57(2H,dd,J=2.8,8.2Hz), 7.67(2H,d,J=8.2 Hz),7.86(2H,dd,J=2.1,8.9 Hz).

[0142]¹³C-NMR(CDCl₃): δ12.2,14.0,22.5,27.3,27.5,28.8,31.6,33.6(d,J=69.7Hz), 122.8(d,J=9.8 Hz),123.5(dd,J=4.0,13.3 Hz),132.8(dd,J=9.9,16.9 Hz),132.9(dd,J=29.7,94.8 Hz),136.3,139.8(dd,J=11.6,18.3 Hz).

[0143]³¹P-NMR(CDCl₃): δ49.2.

[0144] m.p.: 84.4-85.2° C.

[0145] Elementary Analysis: Calculated as C₂₀H₂₃OPBr₂: C, 51.09; H,4.93.

[0146] Found: C, 50.89; H, 5.14.

Example 13

[0147] In the same manner as in Example 1, obtained was 0.229 g (0.74mmol in terms of the monomer unit) of a polymer having repeating unitsof a 9-(3-ethylhexyl)-9-oxo-9-phosphafluorene-2,7-diyl group (of formula[III] where R is 3-ethylhexyl group), for which, however, used was 0.470g (1.0 mmol) of 2,7-dibromo-9-(3-ethylhexyl)-9-oxo-9-phosphafluoene (offormula [VI] where R is 3-ethylhexyl group and X is bromine) in place of2,7-dibromo-9-nonyl-9-oxo-9-phosphafluoene in Example 1. Thus obtained,the polymer is a novel compound not disclosed in any literature.Calculated through gel permeation chromatography method (GPC method),its number-average molecular weight was 5680 and its weight-averagemolecular weight was 6250.

[0148] Its NMR spectral data are mentioned below.

[0149]¹H-NMR(CDCl₃):δ0.76(6H,brs),1.21(4H,brs),1.33(4H,brs),1.67(1H,brs),2.16(2H,brs),7.85(4H,brs),8.10(2H,brs).

[0150]³¹P-NMR(CDCl₃): δ44.1.

Example 14

[0151] (Reaction with Catalytic Amount of Ni Salt/Zinc):

[0152] In a nitrogen atmosphere, 0.0016 g (0.0125 mmol) of nickelchloride, 0.0020 g (0.00125 mmol) of α,α′-dipyridyl, 0.0031 g (0.50mmol) of zinc powder, and 0.00627 g (0.125 mmol) of2,7-dibromo-9-nonyl-9-oxo-9-phosphafluorene (of formula [VI] where R isnonyl group and X is bromine) were dissolved in N,N-dimethylformamide,to which was added 1.6 μL (0.0125 mmol) of chlorotrimethylsilane, andstirred under heat at 100° C. for 48 hours. The reaction mixture waspoured into 20 mL of 0.5 diluted hydrochloric acid, and the resultingpowder was taken out through filtration. The powder was washed with 10mL of water, then dissolved in 1 mL of chloroform, and reprecipitated in10 mL of methanol to thereby obtain 33 mg (0.108 mmol in terms of themonomer unit) of a polymer having repeating units of a9-nonyl-9-oxo-9-phosphafluorene-2,7-diyl skeleton (of formula [III]where R is nonyl group). Calculated through GPC method, thenumber-average molecular weight of the polymer was 2730 and theweight-average molecular weight thereof was 3720.

Example 15

[0153] In the same manner as in Example 4, obtained was 0.264 g (0.47mmol in terms of the monomer unit) of a polymer having in the backbone a9-(2-octyl)-9-oxo-9-phosphafluorene-2,7-diyl group and a2,5-dihexyloxy-1,4-phenylene group (of formula [IV] where R is 2-octylgroup and Ar is 2,5-dihexyloxy-1,4-phenylene group), for which, however,used was 0.235 g (0.50 mmol) of2,7-dibromo-9-(2-octyl)-9-oxo-9-phosphafluorene (of formula [VI] where Ris 2-octyl group and X is bromine) in place of2,7-dibromo-9-nonyl-9-oxo-9-phosphafluorene in Example 4, and used were0.0058 g (0.0050 mmol) of tetrakis(triphenylphosphine)palladium, 0.184 g(0.50 mmol) of 2,5-dihexyloxy-1,4-phenylenediboronic acid, 1.0 g oftripotassium phosphate and 5 mL of N,N-dimethylformamide. Thus obtained,the polymer is a novel compound not disclosed in any literature.Calculated through GPC method, the number-average molecular weight ofthe polymer was 19400 and the weight-average molecular weight thereofwas 22000. Calculated through elementary analysis, the mean molecularweight of the polymer was 13400.

[0154] The NMR spectral data and elementary analysis data of the polymerare mentioned below.

[0155]¹H-NMR(CDCl₃): δ0.87(9H,brs),1.08(3H,dd,J=6.1,18.2Hz),1.36(18H,brs),1.73(7H,m),2.00(1H,brs),2.33(2H,brs),2.95(4H,brs),7.09(2H,s),7.85(2H,m),7.96(2H,m),8.04(2H,m).

[0156]³¹P-NMR(CDCl₃): δ51.3.

[0157] Elementary Analysis: Calculated as n=22 (C₈₅₆H₁₁₄₅O₆₇P₂₃Br₂): C,76.84; H, 8.63; Br, 1.20.

[0158] Found: C, 76.38; H, 8.65; Br, 1.20.

Example 16

[0159] In the same manner as in Example 10, obtained was 11.7 g (24.8mmol) of 2,7-dibromo-9-(3-ethylhexyl)-9-oxo-9-phosphafluoene (of formula[VI] where R is 3-ethylhexyl group), for which, however, used was 12.5 g(40.0 mmol) of 9-(3-ethylhexyl)-9-oxo-9-phosphafluorene (of formula [IX]where R is 3-ethylhexyl) in place of 9-oxo-9-phospha-9-propylfluorene inExample 10. Thus obtained, the compound was a colorless acicularcrystal, and is a novel compound not disclosed in any literature.

[0160] Its IR and NMR spectral data, melting point and elementaryanalysis data are mentioned below.

[0161]IR(KBr):2958.3,2923.6,2856.1,1442.4,1390.4,1184.1,1085.7,817.7cm⁻¹.

[0162]¹H-NMR(CDCl₃): δ0.79(3H,t,J=7.4 Hz)0.83(3H,t,J=7.0Hz),1.12-1.17(4H,m),1.28-1.32(2H,m),1.37-1.43(2H,m),1.65-1.71(1H,m)2.01-2.13(2H,m),7.60(2H,dd,J=2.9,8.2 Hz),7.69(2H,d,J=8.3 Hz),7.92(2H,dd,J=1.6,9.1 Hz).

[0163]¹³C-NMR(CDCl₃): δ10.3,14.0,22.7,27.4(d,J=8.8 Hz),28.8,34.0(d,J=8.2Hz), 34.3(d,J=69.2 Hz),34.4(d,J=3.1 Hz),122.7(d,J=10.3Hz),123.6(dd,J=4.1,13.5 Hz), 132.5(d,J=10.4 Hz),134.5(dd,J=15.5,97.3Hz),136.2,138.9(dd,J=3.1,19.7 Hz).

[0164]³¹P-NMR(CDCl₃): δ42.7.

[0165] m.p.: 139.1-139.8° C.

[0166] Elementary Analysis: Calculated as C₂₀H₂₃OPBr₂: C, 51.09; H,4.93.

[0167] Found: C, 50.86; H, 5.14.

Example 17

[0168] The solubility (1 mg polymer/1 mL solvent) of the polymersobtained in Examples 1 to 9, 13 and 15 in different solvents wasevaluated.

[0169] The results are shown in Tables 1 to 4. Regarding the criteriafor evaluation, soluble samples are indicated by (⊚); partly solublesamples are by {◯ or Δ, but ◯>Δ in point of the solubility); andinsoluble samples are by (x). TABLE 1 Solubility of Polymers SolventPolymer CHCl₃ THF methanol toluene Example 1 ⊚ ◯ Δ x Example 2 ⊚ ◯ Δ xExample 3 Δ Δ x x

[0170] TABLE 2 Solubility of Polymers Solvent Polymer CHCl₃ THF ethanoltoluene Example 4 ⊚ ⊚ ◯ Δ Example 5 ⊚ ◯ Δ x Example 6 ⊚ Δ x x

[0171] TABLE 3 Solubility of Polymers Solvent Polymer CHCl₃ THF methanoltoluene Example 7 ⊚ Δ Δ x Example 8 ◯ Δ Δ x Example 9 ◯ Δ x x

[0172] TABLE 4 Solubility of Polymers Solvent Polymer CHCl₃ THF methanoltoluene Example 13 ⊚ Δ x x Example 15 ⊚ ◯ Δ x

Example 18

[0173] The optical properties of the polymers obtained in Examples 1 to9, 13 and 15 were evaluated. The matters tested for these are theabsorption peak wavelength in the UV range (UVλmax), the molarextinction coefficient per the monomer unit (ε), the fluorescentspectrum peak wavelength in UV exposure (EMλmax), and the quantumefficiency in solution.

[0174] The results are given in Table 5. TABLE 5 Optical Properties ofPolymers Optical Properties Solution in CHCl₃ Thin Film UVλmax EMλmax εquantum UVλmax EMλmax Polymer (nm) (nm) (M⁻¹cm⁻¹) efficiency (nm) (nm)Example 1 387 443 24700 0.59 398 447 Example 2 390 444 23900 0.63 398475 Example 3 383 442 17553 0.73 * * Example 4 384 431 25700 0.76 390472 Example 5 386 433 29400 0.72 395 465 Example 6 378 413 31800 0.81386 457 Example 7 400 456 16300 0.74 433 539 Example 8 408 455 191000.78 420 536 Example 9 400 456 17600 0.77 408 538 Example 13 390 44328500 0.81 399 481 Example 15 386 432 29200 0.68 387 465

[0175] As is known from Table 5, the polymers obtained in Examples 1 to9, 13 and 15 all emit fluorescence having a peak wavelength in thevisible light range in any form of solution in CHCl₃ and thin film, andtheir quantum efficiency in solution in CHCl₃ is high, falling between0.59 and 0.81.

Example 19

[0176] (Electrochromic Element Formed of Polymer):

[0177] This is to demonstrate the spectral electrochemical response ofthe polymer obtained in Example 4. One mg of the polymer was dissolvedin 200 μL of dichloroethane, and the resulting polymer solution was caston a commercially-available transparent electrode (50×5 mm) to prepare aworking electrode. This was disposed in a quartz cell along with acounter electrode (platinum plate) and a reference electrode (silver,silver ion electrode). With that, the cell was filled with a supportingelectrolyte, tetrabutylammonium perchlorate, and a solvent, dewateredacetonitrile. The cell was driven, and the color change of the polymerowing to the potential change in the cell was detected with aspectrophotometer. As a result, it was found that the thin film of thepolymer of Example 4 was pale yellow in neutral but changed from paleyellow to deep violet with the increase in the potential applied to thecast film of the polymer. With the change, the UV absorption bandintrinsic to the polymer that had existed at around 390 nm disappeared,and a novel visible light absorption band appeared at around 570 nm.

[0178] Industrial Applicability

[0179] The present invention provides a polymer which contains in thebackbone a 9-oxo-9-phosphafluorene-2,7-diyl skeleton or a combination ofthe skeleton and an arylene or vinylene group and which is useful, forexample, as a component of a luminescent element or electrochromicelement, and provides a process for producing the polymer.

[0180] The invention also provides a 2,7-dihalo-9-oxo-9-phosphafluorenecompound which is useful, for example, as a monomer for producingfunctional polymers, and provides a process for producing the compound.

1. A polymer that contains in the backbone a9-oxo-9-phosphafluorene-2,7-diyl skeleton and a vinylene skeleton of thefollowing general formula [I]:

[wherein —Q— represents a single bond, —Ar— (Ar is an arylene group), ora vinylene group of the following general formula [II]:

(in which R′ represents a hydrogen atom, an optionally-substitutedalkyl, cycloalkyl, aryl or aralkyl group, a cyano group, or analkoxycarbonyl group, and it may bond to any carbon of the olefin chainin the formula); R represents a hydrogen atom, or anoptionally-substituted alkyl, cycloalkyl, aralkyl, aryl, alkoxy,cycloalkyloxy, aralkyloxy or aryloxy group; and n indicates an integerof from 3 to 30000].
 2. The polymer as claimed in claim 1, for which —Q—in formula [I] is a single bond and which is represented by thefollowing general formula [III]:

(wherein R and n have the same meanings as above).
 3. The polymer asclaimed in claim 1, for which —Q— in formula [I] is —Ar— and which isrepresented by the following general formula [IV]:

(wherein Ar, R and n have the same meanings as above).
 4. The polymer asclaimed in claim 1, for which —Q— in formula [I] is the vinylene groupof formula [II] and which is represented by the following generalformula [V]:

(wherein R′, R and n have the same meanings as above).
 5. A process forproducing the polymer of claim 1, which comprises dehalo-polycondensinga 2,7-dihalo-9-oxo-9-phosphafluoene of the following general formula[VI]:

(wherein R and X have the same meanings as above), or reacting it withan arylenebisboronic acid followed by polycondensing the resultingintermediate, or polycondensing it with an olefin.
 6. The productionprocess as claimed in claim 5, wherein the polycondensation is effectedin the presence of a transition metal-based chemical substance.
 7. Theproduction process as claimed in claim 6, wherein the transitionmetal-based chemical substance is a low-valence transition metal-basedchemical substance.
 8. The production process as claimed in claim 7,wherein the polycondensation is effected in the presence of thelow-valence transition metal-based chemical substance formed by adding areducing agent to a transition metal-based chemical substance of whichthe valence is not low.
 9. The production process as claimed in any ofclaims 6 to 8, wherein the transition metal is nickel.
 10. Theproduction process as claimed in any of claims 6 to 8, wherein thetransition metal is palladium.
 11. A process for producing the polymerof claim 2, which comprises dehalo-polycondensation of the2,7-dihalo-9-oxo-9-phosphafluorene of formula [VI].
 12. The productionprocess as claimed in claim 11, wherein the polycondensation is effectedin the presence of a transition metal-based chemical substance.
 13. Theproduction process as claimed in claim 12, wherein the transitionmetal-based chemical substance is a low-valence transition metal-basedchemical substance.
 14. The production process as claimed in claim 13,wherein the polycondensation is effected in the presence of thelow-valence transition metal-based chemical substance formed by adding areducing agent to a transition metal-based chemical substance of whichthe valence is not low.
 15. The production process as claimed in any ofclaims 12 to 14, wherein the transition metal is nickel.
 16. A processfor producing the polymer of claim 3, which comprises polycondensationof the 2,7-dihalo-9-oxo-9-phosphafluorene of formula [VI] with anarylenebisboronic acid of the following general formula [VII]:(HO)₂B—Ar—B(OH)₂  [VII] wherein Ar has the same meaning as above. 17.The production process as claimed in claim 16, wherein thepolycondensation is effected in the presence of a palladium catalyst.18. The production process as claimed in claim 17, wherein the palladiumcatalyst is a low-valance complex catalyst.
 19. The production processas claimed in claim 17, wherein the palladium catalyst is a divalentcomplex with a ligand of a tertiary phosphine or tertiary phosphite. 20.The production process as claimed in claim 17, wherein the palladiumcatalyst is a precursor complex capable of being readily converted intoa low-valence complex in the reaction system.
 21. The production processas claimed in claim 17, wherein the palladium catalyst is a low-valencecomplex with a ligand of tertiary phosphine and/or tertiary phosphitethat is formed from a combination of a palladium complex not having aligand of a tertiary phosphine or tertiary phosphite, and a tertiaryphosphine and/or a tertiary phosphite in the reaction system.
 22. Aprocess for producing the polymer of claim 4, which comprisespolycondensation of the 2,7-dihalo-9-oxo-9-phosphafluorene of formula[VI] with an olefin of the following general formula [VIII]:

(wherein R′ has the same meaning as above).
 23. The production processas claimed in claim 22, wherein the olefin is ethylene.
 24. Theproduction process as claimed in claim 22 or 23, wherein thepolycondensation is effected in the presence of a transition metal-basedchemical substance.
 25. The production process as claimed in claim 24,wherein the transition metal-based chemical substance is a low-valencetransition metal-based chemical substance.
 26. The production process asclaimed in claim 25, wherein the polycondensation is effected in thepresence of the low-valence transition metal-based chemical substanceformed by adding a reducing agent to a transition metal-based chemicalsubstance of which the valence is not low.
 27. The production process asclaimed in any of claims 24 to 26, wherein the transition metal ispalladium.
 28. The production process as claimed in claim 27, whereinthe palladium catalyst is a divalent complex with a ligand of a tertiaryphosphine or tertiary phosphite.
 29. The production process as claimedin claim 27, wherein the palladium catalyst is a precursor complexcapable of being readily converted into a low-valence complex in thereaction system.
 30. The production process as claimed in claim 27,wherein the palladium catalyst is a low-valence complex with a ligand oftertiary phosphine and/or tertiary phosphite that is formed from acombination of a palladium complex not having a ligand of a tertiaryphosphine or tertiary phosphite, and a tertiary phosphine and/or atertiary phosphite in the reaction system.
 31. A luminescent orelectrochromic element that comprises a polymer having a9-oxo-9-phosphafluorene-2,7-diyl skeleton of the following generalformula [I]:

(wherein —Q—, R and n have the same meanings as above).
 32. A processfor producing a 2,7-dihalo-9-oxo-9-phosphaflorene compound of thefollowing general formula [VI]:

(in which R has the same meaning as above; and X represents a halogenatom), which comprises halogenating a 9-oxo-9-phosphafluorene of thefollowing general formula [IX]:

(in which R represents a hydrogen atom, or an optionally-substitutedalkyl, cycloalkyl, aralkyl, aryl, alkoxy, cycloalkyloxy, aralkyloxy oraryloxy group), with a halogen molecule.
 33. The production process asclaimed in claim 32, wherein the halogenation is effected in thepresence of a Lewis acid catalyst.
 34. The production process as claimedin claim 33, wherein the Lewis acid catalyst is a metal or a metal salt.35. The production process as claimed in claim 34, wherein the metal toform the Lewis acid catalyst is iron, aluminium or antimony.
 36. A2,7-dihalo-9-oxo-9-phosphafluoene compound of the following generalformula[VI]

(wherein R and X have the same meanings as above).